Abstract

Two-dimensional boron nitride (2D-BN) materials doped with metallic atoms are suitable candidates for the oxygen reduction reaction (ORR) to replace Pt-based catalysts. In this study, a series of model 2D-BN materials doped with metallic atoms were designed to uncover the relationship between ORR activity and metallic dopants. A volcano curve correlation was derived between ORR overpotential and the adsorption free energy values of *OH. Only the doped structures, located at the top of the volcano curve, exhibit optimized activity. Through analyzing the dynamic results, the ORR was found to occur only via the 4e− pathway on Co doped 2D-BN materials with the activation energy of 0.30 eV, which is lower than that achieved with the state-of-the-art Pt-based catalysts (0.79 eV). Furthermore, based on the calculations of electronic structure properties, we find that the small highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap is more beneficial to the 4e− pathway and prove that the binding strength between metallic atoms-doped 2D-BN materials and oxygenated intermediates is regulated by the HOMO of the metallic dopant consisting non-bonding or delocalized orbitals. These results provide an effective method to facilitate the design of new BN-based materials with high electrocatalytic performances besides the ORR performance.

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